Reduced charge montmorillonite pigment for sensitizing record material

Abstract

A reduced charge montmorillonite pigment useful as a color-former in record material, especially pressure-sensitive carbonless copying record systems. The pigment is produced by replacing exchangeable cations of a selected dioctahedral montmorillonite crude clay (exemplified by certain bentonite clays) with a predetermined amount of lithium ions, mildly heating the lithium-exchanged montmorillonite to collapse irreversibly the montmorillonite structure, and grinding the heat-treated material to pigment-size particles, the grinding preferably being carried out in a fluid energy mill. When the pigment particles are coated on paper, the coated sheets produce stabilized intense images when printed with a solution of crystal violet lactone (CVL) dye precursor and thus may be used in record material with CVL without employing secondary slow acting dyes such as benzoyl leuco methylene blue. The sheets are also useful with other colorless or substantially colorless dye precursors.

We claim: 
     
       1. A sensitizing pigment for record material comprising micron-size particles of a mixed layer smectite, the lattice of which is partially dioctahedral montmorillonite and partially trioctahedral such as saponite or hectorite, and wherein the proportion of trioctahedral is small, said mixed layer smectite having been subjected to ion-exchange treatment with a preselected quantity of lithium ions followed by heat treamtnet to collapse irreversibly the dioctahedral montmorillonite structure, said particles being capable when coated on paper of producing a stable intense blue image when printed with a solution of crystal violet lactone in an organic solvent. 
     
     
       2. The pigment of claim 1 wherein said particles are essentially all finer than 15 microns and are predominatly in the size range of 1/2 to 5 microns. 
     
     
       3. The pigment of claim 2 wherein said particles contain from about 0.5% to 4% Li 2  O based on the weight of the particles after being heated to costant weight at 1800° F. 
     
     
       4. The pigment of claim 3 wherein said particles contain from about 0.8% to 3% Li 2  O. 
     
     
       5. Finely divided particles of reduced charge dioctahedral montmorillonite clay pigment obtained by ion-exchanging a crude mixed layer smectite clay, the lattice of which is partially dioctahedral montmorillonite and partially trioctahedral such as saponite or hectorite, and wherein the smectite clay contains more than 70% dioctahedral montmorillonite, with from about 60 to 120 meq./100 g. of lithium ions, said crude clay containing less than about 7% by weight hydrated silica, heating the ion-exchanged clay at a temperature in the range of about 160°C. to 300° C. to collapse irreversibly the dioctahedral montmorillonite structure, and fluid energy milling the heated material, said pigment being capable when coated on paper of producing a stable intense blue color when contacted with a solution of crystal violet lactone in an organic solvent, said pigment being chracterized further by the fact that a conventional X-ray pattern exhibits a basal planar spacing at 9.4 to 10.7A. which does not increase when the pigment is exposed to saturated water vapor and an expansion to about 17.3A. when ethylene glycol is used, said pigment having a base exchange capacity in the range of 20 to 50 meq./100 g., a free moisture content in the range of 1 to 3% by weight, being capable of being prepared into a dispersed aqueous slurry which exhibits substantially Newtonian rheological behavior at a solids level of 40%, a surface area in the range of 40 to 80 m 2  /g. as determined by nitrogen adsorption and a G.E. brightness of at least 60%. 
     
     
       6. The pigment of claim 5 wherein said particles contain from about 0.5% to 4% Li 2  O, based on the weight of the particles after being heated to constant weight at 1800° F. 
     
     
       7. The pigment of claim 6 wherein said particles contain from about 0.8% to 3% Li 2  O, based on the weight of the particles after being heated to constant weight at 1800° F. 
     
     
       8. A method for preparing a sensitized image-developing pigment for a record material system which comprises providing crude mixed layer smectite clay, the lattice of which is partially dioctahedral montmorillonite and partially trioctahedral such as saponite or hectorite, and wherein the smectite clay contains more than 70% dioctahedral montmorillonite, partially exchanging exchangeable cations in said clay with lithium ions in amount corresponding to from 60% to 125% of the baase-exchange capacity of the crude clay, said crude clay containing less than 7% by weight hydrated silica, heating the ion-exchanged clay at a temperature in the range of about 160° C. to 300° C. to collapse irreversibly the dioctahedral montmorillonite structure and then grinding the resulting partially reduced charge montmorillonite in a fluid energy mill until the partices are finer than 15 microns. 
     
     
       9. The method of claim 8 wherein sufficient lithium ions are added to produce said particles containing from 0.5 to 4% by weight Li 2  O based on the weight of the particles after being heated to constant weight at 1800° F. 
     
     
       10. The method of claim 8 wherein sufficient lithium ions are added to produce particles containing from about 0.8 to 3% by weight Li 2  O. 
     
     
       11. A method for producing a pigment useful in the production of record material based on the use of an encapsulated solution of crystal violet lactone, which comprises providing a mixed layer smectite clay, the lattice of which is partially dioctahedral montmorillonite and partially trioctahedral such as hectorite or saponite, and wherein the clay contains more than 70% dioctahedral montmorillonite, said clay containing exchangeable alkaline earth cations, containing less than 7% hydrated silica and having a G.E. brightness above 60%, partially exchanging exchangeable cations in said clay with from about 60 to 120 meq./100 g. of lithium ions, heating the clay thus treated at a temperature in the range of 160° C. to 250° C. until the structure of the dioctahedral montmorillonite is collapsed, as evidenced by the fact that the product has a basal planar spacing in the range of about 9.6 to 10.0 A., and grinding in a fluid energy mill to produce particles of reactive pigment that are essentially all finer than 15 microns and predominantly in the size range of 1/2 to 5 microns. 
     
     
       12. A pigment mixture for sensitizing record material comprising a mixture of the pigment of claim 1 with a pigment selected from the group consisting of calcium carbonate, kaolin and mixtures thereof. 
     
     
       13. The pigment mixture of claim 12 which consists of the pigment of claim 1 with from about 30% to 40% by weight of kaolin clay. 
     
     
       14. The pigment mixture of claim 12 which consists of about 70 parts by weight of the pigment of claim 1, about 20 parts by weight of calcium carbonate and about 10 parts by weight of kaolin clay.